WO2015189762A2 - Organic resin laminate - Google Patents
Organic resin laminate Download PDFInfo
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- WO2015189762A2 WO2015189762A2 PCT/IB2015/054332 IB2015054332W WO2015189762A2 WO 2015189762 A2 WO2015189762 A2 WO 2015189762A2 IB 2015054332 W IB2015054332 W IB 2015054332W WO 2015189762 A2 WO2015189762 A2 WO 2015189762A2
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- meth
- plasma
- coating
- laminate
- acrylate
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- 0 *CCNCC*1CC1 Chemical compound *CCNCC*1CC1 0.000 description 6
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
- B60J1/00—Windows; Windscreens; Accessories therefor
- B60J1/20—Accessories, e.g. wind deflectors, blinds
- B60J1/2094—Protective means for window, e.g. additional panel or foil, against vandalism, dirt, wear, shattered glass, etc.
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
- C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D135/02—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/32—Radiation-absorbing paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2435/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
- C08J2435/02—Characterised by the use of homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2443/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Derivatives of such polymers
- C08J2443/04—Homopolymers or copolymers of monomers containing silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C08J2475/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
Definitions
- This application relates to organic resin laminates having weather resistance and abrasion resistance.
- organic resin substrates are used in a variety of applications.
- recent efforts are devoted to increasing the surface hardness and abrasion resistance of organic resins so that molded organic resins may be applicable to the windows in various vehicles.
- molded organic resins or generally, molded plastic materials have poor surface properties such as abrasion resistance and weather resistance as compared with glass. It is thus attempted to improve their surface properties.
- An embodiment of a method of making an organic resin laminate can comprise: applying a wet coating to an organic resin substrate to form to form an intermediate layer (II) on the substrate, wherein the wet coating comprises a multi-functional (meth)acrylate, a photopolymerization initiator, and a reactive UV absorber having the general formula (1):
- Y 1 and Y 2 can be each independently a substituent group of the general formula (2):
- An embodiment of an organic resin laminate can comprise: an organic resin substrate and a multilayer coating system on a surface of the substrate, said multilayer coating system including a plasma layer formed from polymerization of an organosilicon compound; and an intermediate layer (II) which is a UV cured coating of a reactive UV absorber, a multi-functional (meth)acrylate, and a photopolymerization initiator; wherein the laminate has a Young's Modulus of greater than or equal to 3 GPa as determined by nanoindentation with a maximum load of 1 mN.
- FIG. 1 is a diagram showing the GPC charts of the compound obtained in Synthesis Example 1 and its reactant.
- FIG. 2 illustrates the 1 H-NMR chart of the compound obtained in Synthesis Example 1.
- FIG. 3 illustrates the IR chart of the compound obtained in Synthesis Example 1.
- FIG. 4 is a diagram showing the oxygen permeability charts of the laminates obtained in Example 8.
- a thin film of silicon dioxide or the like can be deposited on a cured layer of wet resin system to achieve the abrasion resistance desired for the automotive windows. Coatings obtained from such a dry coating system achieve improvements in abrasion resistance over the aforementioned wet coating system.
- Expanding thermal plasma (ETP) processes have been used to deposit the dry coatings at high deposition rates.
- the plasma process is suited for coating abrasion resistant coatings in large scale and on large area parts (see, for example, USP 6,110,544, USP 6,948,448, and USP 6,397,776).
- the lamination technology that is arrived at by combining the wet coating process with the dry coating process is found insufficient to prevent organic resin substrates from degradation or discoloration in long-term outdoor exposure tests and accelerated weathering tests.
- Such problems can be overcome by incorporating UV absorbers in wet coating layers for blocking UV.
- these laminate structures comprise an organic resin substrate, a primer layer of an acrylic base coating composition on a surface of the substrate, a silicone hard coat layer formed thereon from a silicone hard coating composition, and a hard silicon oxide layer deposited thereon by a plasma-enhanced CVD process, organic or inorganic UV absorbers can be blended in the primer layer and silicone coat layer.
- the primer layer and the silicone hard coat layer use the step of heat drying at 120°C for about one hour after the coating step.
- this technology is successful in imparting a high level of abrasion resistance and long-term weather resistance, a plurality of heating steps are used. From the aspects of shorter manufacture time, increased yield, and eventual cost saving, it is desirable to simplify the technology.
- a coating composition comprising a multifunctional
- (meth)acrylate compound and a photo-polymerization initiator is coated on a surface of an organic resin substrate, radiation is irradiated to the composition to form a coating which is cross-linked as a result of photo-polymerization of (meth)acrylic groups induced upon radiation exposure, and an oxide layer is formed on the coating by the dry process.
- the photo-curable (meth)acrylic coating composition can be coated and cured to the resin substrate directly without a need for the primer which is essential for the above silicone hard- coat composition. This technology is successful in process simplification, but is still unsatisfactory with respect to long-term weather resistance.
- An embodiment of an organic resin laminate can comprise an organic resin substrate and a multilayer coating system on one surface of the substrate, which exhibits abrasion resistance and weather resistance.
- the multilayer coating system can include a plasma layer in the form of a coating obtained from plasma polymerization of an
- the intermediate layer (II) has a pair of opposed surfaces, with one surface being disposed contiguous to the plasma layer and the other surface being disposed contiguous to the organic resin substrate.
- the wet coating composition comprises (A) a reactive UV absorber of formula (1) defined below, (B) a multi-functional (meth)acrylate, and (C) a photopolymerization initiator.
- An embodiment can include an organic resin laminate that comprises a substrate, such as a molded substrate of polycarbonate resin, and a multilayer coating system on the substrate.
- the multilayer coating system can include an intermediate layer (II) in the form of a cured coating containing a specific reactive UV absorber, and a plasma layer in the form of a coating obtained from plasma polymerization of an organosilicon compound, typically a silicon oxide coating formed by the plasma-enhanced chemical vapor deposition (PECVD) method, which layers can be deposited on the substrate in the described order.
- PECVD plasma-enhanced chemical vapor deposition
- the laminate enables replacement of a system involving 5 layers (i.e., organic resin substrate, cured primer layer, cured silicone layer, and abrasion resistant layer (comprising 2 sublayers)) to be replaced by a new simple system involving 4 layers (i.e., organic resin substrate, intermediate layer (II), and plasma layer as abrasion resistant layer (comprising 2 sublayers)).
- a new simple system involving 4 layers i.e., organic resin substrate, intermediate layer (II), and plasma layer as abrasion resistant layer (comprising 2 sublayers)
- Any of the five layer laminate, or the laminate disclosed herein, can also comprise other layers, such as an ink layer.
- the present laminate possesses visible light transmitting and UV blocking abilities because a specific UV absorber is contained in the intermediate layer (II), and maintains weather resistance over a long term because the UV absorber is fixed in the layer by reacting with a binder, i.e., the UV absorber is prevented from bleeding out of the intermediate layer.
- the laminate is suited for use as windows, for example, windows and windshields in transportation vehicles such as
- the plasma layer can be a coating (e.g., a hard coating) containing silicon, oxygen, carbon and hydrogen, formed by plasma polymerization of an organosilicon compound. More particularly, the hard coating may be formed and stacked by the expanding thermal plasma process. With respect to the expanding thermal plasma technology, reference may be made to JP-A 2009-540124, JP-A 2009-502569, USP 7,163,749, USP 7,056,584, and USP 6,426,125.
- the outermost layer can be deposited using a plasma deposition process (e.g., a low pressure, expanding thermal plasma deposition process).
- a plasma deposition process e.g., a low pressure, expanding thermal plasma deposition process.
- plasma is generated by ionizing a noble gas such as Ar or He.
- the plasma expands in a chamber, typically a low-pressure chamber, where vaporized organosilicon compound is injected. Plasma species react with the organosilicon compound gas to create dissociated molecules, which are
- oxidizing gas is admitted into the chamber so that it may react with the dissociated reactant molecules.
- organosilicon compound which is used to form the plasma layer by the plasma process include, but are not limited to, tetramethoxysilane, tetraethoxysilane, trimethoxysilane, methyltrimethoxysilane, methoxytrimethylsilane, methyl triethoxysilane, hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and 1,3,5,7- tetramethylcyclotetrasiloxane. Octamethylcyclotetrasiloxane is particularly desirable.
- the coating chamber is adapted for a continuous, two-side coating process including a heating station and two coating stations for depositing an inner sub-layer and an outer sub-layer.
- the coating station can include an array of DC plasma arc generators, e.g., in two rows (for example, vertical arrays on opposite sides of the substrate) for coating the entire window surface.
- the deposition rate can be in a range of 100 nanometers/minute (nm/min) to 20,000 nm/min.
- the number of plasma arc generators in a row can be scaled up to completely coat large area substrates, typically windows.
- the plasma layer may include an inner sub-layer (also referred to as first plasma coating) and an outer sub-layer (also referred to as second plasma coating).
- the resin substrate may be heated to a temperature above the ambient temperature in order to achieve adhesion to the inner sublayer. Specifically, the substrate may be heated to a surface temperature of 35 to 100°C prior to the plasma deposition.
- the inner sub-layer contains a higher proportion of organic functional groups than the outer sub-layer, for example, for the purpose of enhancing adhesion.
- the first plasma coating was deposited using a first oxygen flow rate of less than or equal to 100 seem per plasma source, specifically, less than or equal to 50 seem per plasma source, and even more specifically less than or equal to 10 seem per plasma source, and still more specifically, no oxygen flow or an oxygen flow rate of 0 seem (in other words, no oxygen is intentionally introduced in to the coating chamber).
- the second plasma coating was deposited using a second oxygen flow rate of greater than or equal to 250 seem per plasma source, specifically, greater than or equal to 400 seem per plasma source, and even more specifically greater than or equal to 800 seem per plasma source.
- the plasma layer has a Young's Modulus of greater than or equal to 3 GigaPascals (GPa), specifically, 3 GPa to 40 GPa, and more specifically 3 GPa to 15 GPa, as determined by nanoindentation with a maximum load of 1 mN
- the plasma layer can have a total thickness in the range of 2.5 to 5.0 micrometers ( ⁇ ), and more specifically 2.5 to 4.0 ⁇ .
- the intermediate layer (II) can comprise a coating composition comprising (A) a specific reactive UV absorber, (B) a multi-functional (meth)acrylate, and (C) a photopolymerization initiator.
- Y 1 and Y 2" can each independently be a substituent group of the general formula (2).
- R' and R" can each independently be hydrogen, C 1 -C 20 alkyl, C 4 _ C 12 cycloalkyl, C 6 -Ci 2 aryl (optionally substituted with halogen or the like) or C 3 -C 12 heteroaryl (optionally substituted with halogen or the like).
- hydrogen, C 1 -C 20 alkyl, and C 6 -Ci 2 aryl are desirable, and hydrogen and C 1 -C 20 alkyl are most desirable.
- X can be a di-, tri- or tetravalent, linear or branched, saturated hydrocarbon residue, typically C 1 -C 20 alkyl or C 4 -Ci 2 cycloalkyl, which may be separated by at least one element of oxygen, nitrogen, sulfur, and phosphor.
- X is desirably a group having the general formula (3) or (4).
- * 1 bonds to the oxygen in formula (1), *2 bonds to T in formula (1), *3 each independently is hydrogen or bonds to T in formula (1) directly or via a divalent, linear or branched, saturated hydrocarbon group which may be separated by at least one element of oxygen, nitrogen, sulfur, and phosphor, at least one *3 bonds to T directly or via a divalent, linear or branched, saturated hydrocarbon group which may be separated by at least one element of oxygen, nitrogen, sulfur, and phosphor.
- Q is a di- or trivalent, linear or branched, saturated hydrocarbon residue, typically C 1 -C 20 alkyl or C 4 -Ci 2 cycloalkyl, which may be separated by at least one element of oxygen, nitrogen, sulfur, and phosphor.
- Q is desirably a group having the general formula (5) or (6).
- P is (meth)acryloxy, specifically a (meth)acryloxy group having the general formula (11):
- n is an integer of 1 to 3, with the proviso that m and n are not equal to 1 at the same time. Desirably m is 2 and n is 1.
- the method for preparing the reactive UV absorber (A) is not particularly limited.
- the absorber may be synthesized by combination of transesterification and urethanating reactions.
- One method for preparing the reactive UV absorber starts with a precursor having the following formula (7):
- Y 1 , Y 2 , X and n are as defined above.
- those precursors of formula (7) wherein X contains an ester (COO) group can be obtained through the step (i) of effecting transesterification between an ester compound of the following formula (9) and a polyhydric alcohol of the following formula (10) to form a precursor of the following formula (7 a).
- Y 1 and Y2 are as defined above, and R 4 is a monovalent, linear or branched, saturated hydrocarbon group which may be separated by at least one element of oxygen, nitrogen, sulfur, and phosphor.
- R 5 , R 6 and R 7 can each independently be hydrogen, hydroxyl, a monovalent, linear or branched, saturated hydrocarbon group which may be separated by at least one element of oxygen, nitrogen, sulfur, and phosphor, or a monovalent, linear or branched, saturated hydrocarbon group which is terminated with hydroxyl and which may be separated by at least one element of oxygen, nitrogen, sulfur, and phosphor, and at least one of R 5 , R 6 and R 7 is hydroxyl or a monovalent, linear or branched, saturated hydrocarbon group which is terminated with hydroxyl and which may be separated by at least one element of oxygen, nitrogen, sulfur, and phosphor.
- Y 1 , Y 2" and n are as defined above, and X' is a di-, tri- or tetravalent, linear or branched, saturated hydrocarbon residue which contains an ester group and which may be separated by at least one element of oxygen, nitrogen, sulfur, and phosphor, typically a group of formula (4).
- the target compound of formula (1) is prepared through the step (ii) of reacting the precursor of formula (7) with a compound having the following formula (8), specifically reacting a hydroxyl group bonded to X in the precursor of formula (7) with an isocyanate group in the compound of formula (8).
- precursors of formula (7) are known compounds, typically those precursors of formula (7) wherein X is a group of formula (3), they may be prepared by any well-known methods.
- Those precursors of formula (7) wherein X contains an ester (COO) group, typically of formula (4), can be obtained through the step (i) of effecting transesterification between an ester compound of the following formula (9) and a polyhydric alcohol of the following formula (10) to form a precursor of the following formula (7a).
- Y 1 and Y2 are as defined above, and R 4 is a monovalent, linear or branched, saturated hydrocarbon group which may be separated by at least one element of oxygen, nitrogen, sulfur, and phosphor.
- R 5 , R 6 and R 7 are as defined above.
- Y 1 , Y 2" and n are as defined above, and X' is a di-, tri- or tetravalent, linear or branched, saturated hydrocarbon residue which contains an ester group and which may be separated by at least one element of oxygen, nitrogen, sulfur, and phosphor, typically a group of formula (4).
- R 4 is a monovalent, linear or branched, saturated
- hydrocarbon group of 1 to 25 carbon atoms which may be separated by at least one element of oxygen, nitrogen, sulfur, and phosphor.
- examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n- hexyl, isohexyl, cyclohexyl, n-heptyl, isoheptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n- undecyl, and n-dodecyl.
- n-octyl is desirable for availability of starting reactants.
- ester compound of formula (9) is commercially available, for example, under the trade name of Tinuvin 479 from BASF.
- R 5 , R 6 and R 7 can independently be hydrogen, hydroxyl, a monovalent, linear or branched, saturated hydrocarbon group which may be separated by at least one element of oxygen, nitrogen, sulfur, and phosphor, or a monovalent, linear or branched, saturated hydrocarbon group which is terminated with hydroxyl and which may be separated by at least one element of oxygen, nitrogen, sulfur, and phosphor, and at least one of R 5 , R 6 and R 7 is hydroxyl or a monovalent, linear or branched, saturated hydrocarbon group which is terminated with hydroxyl and which may be separated by at least one element of oxygen, nitrogen, sulfur, and phosphor.
- Suitable polyhydric alcohols include pentaerythritol, trimethylolethane, trimethylolpropane, dimethylolpropane, dimethylolbutane, dimethylolpentane, diethylene glocyol, and triethylene glycol, with pentaerythritol and trimethylolpropane being desirable for availability of starting reactants.
- X' is a di-, tri- or tetravalent, linear or branched, saturated hydrocarbon residue which may be separated by at least one element of oxygen, nitrogen, sulfur, and phosphor, specifically an ester-containing group having a residue derived from the compound of formula (10).
- step (i) the reaction of compounds (9) and (10) can be effected at a temperature of 10 to 200°C, desirably at 20 to 180°C. At temperatures below 10°C, the reaction takes a longer time which is undesirable from the aspect of productivity.
- Temperatures above 200°C may promote side reactions to form more by-products and sometimes cause the product to be colored.
- a catalyst may be used to promote the reaction. Any well- known catalysts commonly used in transesterification may be used. For example, tin-based catalysts can be used.
- the catalyst can be used in an amount of 0 to 5% by weight, specifically, greater than 0 to 5% by weight, and more specifically, 1,000 ppm to 3% by weight based on the total weight of the compounds (9) and (10). More than 5% by weight of the catalyst tends to form by-products and cause the product to be colored.
- the compounds (9) and (10) can be used in equimolar amounts although the amounts are not limited thereto.
- a solvent may be used during the reaction of step (i).
- the more desirable solvent is one in which the compound of formula (9) is soluble and which is free of active hydrogen.
- Use of an active hydrogen-bearing solvent is undesired because by-products other than the precursor of formula (7a) can form.
- azeotropic dehydration or dehydration by means of molecular sieves may be carried out.
- the solvent used in step (i) is the same as the solvent used in a coating composition, so that the coating composition can be prepared using the reaction product of step (ii) without a need to remove the solvent therefrom.
- Step (ii) is to react a hydroxyl group bonded to X in the precursor of formula (7) with an isocyanate group in the compound of formula (8) to form the target compound of formula (1).
- Q is a di- or trivalent, linear or branched, saturated hydrocarbon residue which may be separated by at least one element of oxygen, nitrogen, sulfur, and phosphor
- P is (meth)acryloxy
- m is 1 or 2.
- hydrocarbon residue Q examples include -CH 2 -,
- Q can be a group of formula (5) or (6).
- P is (meth)acryloxy, specifically a (meth)acryloxy group having the general formula (11):
- m is 1 or 2, desirably 2. If m exceeds 2, the corresponding compound is difficult to synthesize or not readily available.
- Examples of the compound of formula (8) include 2-acryloyloxyethyl isocyanate, l,l-bis(acryloyloxymethyl)ethyl isocyanate, and 2-methacryloyloxyethyl isocyanate, which are commercially available under the trade name of Karenz AOI, Karenz BEI, and Karenz MOI from Showa Denko K.K.
- step (ii) the reaction of compounds (7) and (8) can be effected at a temperature of 10 to 200°C, specifically at 20 to 180°C. At temperatures below 10°C, the reaction takes a longer time which is undesirable from the aspect of productivity. Temperatures above 200°C may promote side reactions to form more by-products and sometimes cause the product to be colored.
- a catalyst may be used to promote the reaction. Any well- known catalysts commonly used in urethanating reaction may be used, such as tin-based catalysts.
- the catalyst can be used in an amount of 0 to 10,000 ppm, specifically greater than 0 to 10,000 ppm, and more specifically, 100 to 5,000 ppm based on the total weight of the compounds (7) and (8). More than 10,000 ppm of the catalyst tends to form more by-products and cause the product to be colored.
- the compounds (7) and (8) can be used in equimolar amounts although the amounts are not limited thereto.
- the amounts may be adjusted in accordance with the number of hydroxyl groups in compound (7) which are available for reaction with the isocyanate group in compound (8).
- the ratio of compound (7) to compound (8) is adjusted such that no isocyanate group may be left in the reaction product. If the isocyanate group is left, a coating composition comprising the reaction product tends to lose shelf stability.
- a polymerization inhibitor such as p- methoxyphenol may be used in order to restrain polymerization of (meth)acryloxy groups. Polymerization may also be restrained by carrying out the reaction in an atmosphere of air or nitrogen containing 4% oxygen. These polymerization restraining means may be used in combination.
- a solvent may be used during the reaction of step (ii).
- the desirable solvent is one in which the compound of formula (7) is soluble and which is free of active hydrogen.
- Use of an active hydrogen-bearing solvent is undesired because it can react with the isocyanate group in compound (8) to form a by-product.
- azeotropic dehydration or dehydration by means of molecular sieves may be carried out.
- the solvent used in step (ii) is the same as the solvent used in a coating composition, so that the coating composition can be prepared from the reaction product of step (ii) without removing the solvent therefrom.
- the coating composition comprises the reactive UV absorber (A) and the binder precursor (B).
- Component (A) can be used in an amount of 1 to 100 parts, specifically, 5 to 80 parts by weight per 100 parts by weight of component (B). Less than 1 part of component (A) may be insufficient for the resulting laminate to exert satisfactory weather resistance whereas more than 100 parts may detract from the abrasion resistance and substrate adhesion of the resulting laminate.
- Component (B) is a multi-functional (meth)acrylate.
- component (B) which can be used herein can be any component (B) which can be used herein.
- multifunctional (meth)acrylates having a polymerizable unsaturated bond such as, for example, urethane (meth)acrylates, epoxy (meth)acrylates, polyester (meth)acrylates, hydrolyzates and/or condensates of (meth)acryloyloxyalkoxysilanes, and organic/inorganic hybrid (meth)acrylates obtained from hydrolytic condensation of colloidal silica and
- (meth)acryloyloxyalkoxysilane A choice may be made among these in accordance with the required properties of a coating.
- the monofunctional (meth)acrylates include mono- (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl
- (meth)acrylate morpholinyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxyproyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, tricyclodecane (meth)acrylate,
- epoxy poly(meth)acrylates such as epoxy di(meth)acrylate obtained from reaction of bisphenol A diepoxy with (meth)acrylic acid
- hydrolyzates and/or condensates of (meth)acryloyloxyalkoxysilanes, and organic/inorganic hybrid (meth)acrylates obtained from hydrolytic condensation of colloidal silica and (meth)acryloyloxyalkoxysilanes are useful for improving the hardness and durability of a coating.
- Examples can include hydrolyzates or hydrolytic condensates of (meth)acryloyl-containing alkoxysilanes, organic/inorganic hybrid vinyl compounds and organic/inorganic hybrid (meth)acrylates, which can be obtained from (co)hydrolytic condensation of a silane (e.g., vinyltrimethoxysilane, vinyltriethoxysilane, p- styryltrimethoxysilane, 3-(meth)acrloxypropylmethyldimethoxysilane,
- a silane e.g., vinyltrimethoxysilane, vinyltriethoxysilane, p- styryltrimethoxysilane, 3-(meth)acrloxypropylmethyldimethoxysilane
- a plurality of the above-exemplified compounds may be used in combination as component (B), with such a combination being desirable.
- combinations of one or two multifunctional (meth)acrylates with at least one of hydrolyzates or hydrolytic condensates of a (meth)acryloyl-containing alkoxysilane are desirable.
- poly(meth)acrylate having at least five radical polymerizable unsaturated double bonds per molecule, poly[(meth)acryloyloxyalkyl] (iso)cyanurate, (co)hydrolyzate/condensate of (meth)acryloyloxypropylalkoxysilane alone or in admixture with another silane, and organic/inorganic hybrid (meth)acrylate obtained from (co)hydrolytic condensation of colloidal silica and (meth)acrylic functionality alkoxysilane (e.g.,
- (meth)acryloyloxypropylalkoxysilane) alone or in admixture with another silane are more desirable because coatings having improved heat resistance, chemical resistance, durability and adhesion to substrates are obtainable.
- Component (C) is a photopolymerization initiator which is not particularly limited and may be selected in consideration of compatibility and curability in the
- Examples of the initiator (C) include carbonyl compounds such as benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, benzyl dimethyl ketal, 2,2-diethoxyaceto phenone, 1-hydroxycyclohexyl phenyl ketone, methyl phenyl glyoxylate, and
- 2,4,6-trimethylbenzoyldiphenylphosphine oxide 2,4,6-trimethylbenzoylphenylethoxy- phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and bis(2,6-dimethoxy benzoyl)-2,4,4-trimethylpentylphosphine oxide; 2-benzyl-2-dimethylamino-l-(4-morpholino phenyl) butanone-1 and camphorquinone.
- These compounds may be used alone or in admixture of two or more. Any two or more of them may be combined in accordance with the required properties of coatings.
- Component (C) can be used in an amount of 0.1 to 10 parts, specifically, 1 to 8 parts by weight per 100 parts by weight of components (A) and (B) combined. With less than 0.1 part of component (C), the resulting coating may experience a noticeable drop of cure speed and losses of abrasion resistance and substrate adhesion. With more than 10 parts of component (C), a cured coating may be colored or degraded in weather resistance.
- the wet coating composition of which the intermediate layer (II) is made may further contain one or more additives.
- additives include UV absorbers other than component (A), organic solvents, antifouling agents, water repellents, leveling agents, colorants, pigments, antioxidants, anti-yellowing agents, bluing agent, defoamers, thickeners, anti-settling agents, antistatics, surfactants, tackifiers, IR absorbers, photo stabilizers, curing catalysts, and metal oxide fine particles.
- the coating composition can comprise at least one additive selected from among antifouling agents, water repellents, leveling agents, colorants, pigments, tackifiers, IR absorbers, photo stabilizers, curing catalysts other than the photopolymerization initiator, metal oxide fine particles other than the organic/inorganic hybrid (meth)acrylates (which may also be referred to as the colloidal silica surface treated with a (meth)acrylic functional alkoxysilane), and UV absorbers other than component (A).
- additives selected from among antifouling agents, water repellents, leveling agents, colorants, pigments, tackifiers, IR absorbers, photo stabilizers, curing catalysts other than the photopolymerization initiator, metal oxide fine particles other than the organic/inorganic hybrid (meth)acrylates (which may also be referred to as the colloidal silica surface treated with a (meth)acrylic functional alkoxysilane), and UV absorbers other than component (A).
- the metal oxide fine particles include silica, zinc oxide, titanium oxide, cerium oxide, and combinations comprising at least one of the foregoing.
- the metal oxide fine particles are desirably of nano size (e.g., less than 1 micrometer).
- Metal oxide nanoparticles may be added in an appropriate amount when it is desired to increase the hardness and abrasion resistance of the laminate or enhance the UV absorption capability thereof.
- Such particles have a particle size (or length) of nano (i.e., nanometer, (nm)) or submicron order, specifically up to 500 nm, more specifically 5 nm to 200 nm.
- the nanoparticles take the form of a dispersion wherein nanoparticles are dispersed in a medium such as water or organic solvent.
- a medium such as water or organic solvent.
- suitable silica dispersions are commercially available as Snowtex-O, OS, OL and Methanol Silica Sol from Nissan Chemical Industries, Ltd.
- Nanoparticles of zinc oxide, titanium oxide, and cerium oxide, those having minimal or no photocatalytic activity can be used.
- oxide nanoparticles have a UV- screening function as well as a photocatalyst function. If oxide nanoparticles having high photocatalytic activity are used in a coating composition, the coating can crack due to degradation of the binder by the photocatalyst function. If nanoparticles having minimal or no photocatalytic activity are used, then cracking is restrained.
- the photocatalytic activity may be evaluated by measuring a change of absorbance by photodegradation of methylene blue.
- 0.15 g calculated as oxide nanoparticle solid is added to 20 g of a methylene blue solution in a water/methanol weight ratio (1: 1) having a methylene blue concentration of 0.01 millimole per liter (mmol/L).
- the solution is irradiated with black light at power of 15 watt (W) and distance of 100 millimeter (mm) from the solution to light for 12 hours. Thereafter, the solution was centrifuged at 3,000 revolutions per minute (rpm) for 15 minutes to collect the supernatant, and the absorbance of methylene blue at 653 nanometers (nm) is measured by a UV/visible spectrophotometer.
- the oxide nanoparticles should have a photocatalytic degradability (PD) of less than or equal to 25%.
- oxide nanoparticles having a minimal photocatalyst activity include surface-coated oxide nanoparticles which can be obtained by coating surfaces of oxide nanoparticles with an oxide (e.g., silica) or hydroxide, or by surface treating with a hydrolyzable silane.
- Examples of the surface-coated oxide nanoparticles include those in which oxide nanoparticles are provided with an oxide coating by using an alkoxide of Al, Si, Zr or Sn and effecting hydrolysis, and those obtained by using a sodium silicate aqueous solution, and neutralizing the solution for causing oxide or hydroxide to precipitate on surfaces, and optionally, heating the precipitated oxide or hydroxide for enhancing
- Such oxide nanoparticles are commercially available as Nano-TekTM ZNTANB 15 wt%-E16, E34, and RTTDNB 15 wt%-E68, E88 by C.I. Kasei Co., Ltd.
- the nanoparticulate metal oxide may be added in an amount of 0 to 50 parts by weight and if used, specifically, greater than 0 to 50 parts by weight, and more specifically, 5 to 40 parts by weight (pbw) per 100 parts by weight as solids of components (A), (B) and (C) combined. More than 50 pbw of the metal oxide may detract from adhesion to substrates.
- an organic UV absorber other than component (A) may be compounded.
- the UV absorber comprises organic UV absorber(s) which are compatible with the wet coating composition and have a low volatility.
- organic UV absorber(s) have a molecular weight of greater than or equal to 300 and a weight retention of at least 90% when held at 120 °C for 24 hours in an open state.
- Those compound derivatives whose main skeleton is hydroxy benzophenone, benzotriazole, cyanoacrylate or triazine are desirable.
- polymers such as vinyl polymers and copolymers, having these UV absorbers incorporated in a side chain, and silyl-modified organic UV absorbers and (partial) hydrolytic condensates thereof.
- additional UV absorbers include 2,4-dihydroxybenzophenone, 2,2' ,4,4'- tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy benzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone,
- the additional organic UV absorber may be added in an amount of 0 to 50 parts, specifically, greater than 0 to 50 parts, more specifically, 0.3 to 15 parts, and even more specifically, 0.3 to 5 parts by weight per 100 parts by weight of the solids in the wet coating composition.
- the additional organic UV absorber bleeds out since the organic UV absorber free of a reactive (meth)acrylic group does not react with the binder precursor and is not fixed in the intermediate layer.
- the bled-out UV absorber may adversely affect the adhesion between intermediate layer (II) and plasma layer.
- fluorochemical or silicone surfactants such as Fluorad FC-4430 (Sumitomo 3M) and KP-341 (Shin-Etsu Chemical Co., Ltd.) may be added in effective amounts.
- crosslinking cure catalysts such as Neostann U-810 (Nitto Kasei Co., Ltd.), B-7 (Nippon Soda Co., Ltd.) and Orgatix ZA-60 and TC-200 (Matsumoto Fine Chemical Co., Ltd.) may be added in catalytic amounts.
- Any suitable organic solvent may be selected in accordance with a particular application method.
- a choice may be made from alcohol solvents such as isobutanol, glycol solvents such as propylene glycol monomethyl ether, ester solvents such as n-butyl acetate, ketone solvents such as methyl isobutyl ketone, aromatic solvents such as toluene, and combinations thereof.
- the solvent is used in such amounts that the coating composition may have a viscosity of up to 20 mPa- s where spray coating is employed, or a viscosity of up to 100 mPa- s where shower flow coating or dipping is employed.
- the solvent should be carefully selected while taking into account the solubility of additives.
- the thickness of intermediate layer (II) is not particularly limited, the intermediate layer can have a thickness of 0.1 to 50 ⁇ .
- a thickness in the range of 1 to 30 ⁇ is desirable for ensuring that the coating layer has hardness, abrasion resistance, long- term stable adhesion and crack resistance. If the thickness is less than 0.1 ⁇ , the coating may become defective or fail to impart a satisfactory UV absorbing capability. If the thickness exceeds 50 ⁇ , the coating is likely to crack.
- the wet coating composition may be applied to the substrate by any ordinary coating technique. Suitable coating techniques include brush coating, spray coating, dipping, flow coating, roll coating, curtain coating, spin coating, and knife coating.
- the coating may be dried before the intermediate layer (II) is completed.
- the drying is not particularly limited as long as the solvent is removed.
- the coating is heated at a temperature below the heat resistant temperature of the substrate.
- the coating can be heated at a temperature of 15 to 120°C for 1 to 20 minutes.
- the wet coating composition is cured by light exposure.
- the source and dose of exposure are not particularly limited.
- Exemplary exposure sources include low, medium, high and ultra-high pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, fluorescent lamps, tungsten lamps and sunlight.
- the exposure dose can be in a range of 100 to 10,000 milliJoule per square centimeter (mJ/cm ) at 365 nm, more specifically, 300 to 5,000 mJ/cm at 365 nm.
- the composition may be applied to the substrate surface directly or via another coating layer, if desired, such as a primer layer, UV-absorbing layer, printing layer, recording layer, thermal barrier layer, adhesive layer or inorganic evaporated layer.
- another coating layer may be formed, if desired, such as an adhesive layer, UV-absorbing layer, printing layer, recording layer, thermal barrier layer, adhesive layer, inorganic evaporated layer, water and/or oil repellent layer or hydrophilic anti-fouling layer.
- the substrate used herein may be made of any plastic materials (e.g., organic resin substrate), for example, desirably polycarbonate, polystyrene, polyesters, acrylic resins, modified acrylic resins, urethane resins, thiourethane resins, polycondensates of halogenated bisphenol A and ethylene glycol, acrylic urethane resins, halogenated aryl- containing acrylic resins, sulfur-containing resins, and combinations comprising at least one of the foregoing.
- plastic materials e.g., organic resin substrate
- resin substrates which have been surface treated, specifically by conversion treatment, corona discharge treatment, plasma treatment, acid or alkaline treatment, or combination treatment comprising at least one of the foregoing are also useful.
- the substrate may be a monolithic or multilayer structure. Included are laminated substrates comprising a base resin substrate and a surface layer formed thereon from a resin of different type from the base resin. Exemplary laminated substrates include those consisting of a monolithic substrate of plastic material (typically, transparent plastic material such as polycarbonate) and a multilayer coating deposited directly on the substrate surface in physical contact therewith. Another embodiment is a substrate consisting of a plurality of layers, which is prepared by co-extrusion or lamination technique, for example. Examples of the laminated substrate consisting of a plurality of layers include those having a cap layer (e.g., acrylic resin layer and/or urethane resin layer) and a plastic layer formed by co- extrusion or lamination technique.
- a cap layer e.g., acrylic resin layer and/or urethane resin layer
- the substrate of multilayer structure is typically a substrate comprising a plastic substrate and a UV-absorbing cap layer, with examples including a multilayer substrate having a polycarbonate base resin substrate and a cap layer of acrylic resin or urethane resin, and a multilayer substrate having a polyester base resin substrate and a cap layer of acrylic resin.
- These multilayer substrates are typically prepared by co-extrusion or lamination technique.
- the laminate is characterized by abrasion resistance.
- An index of abrasion resistance is a delta haze value ( ⁇ ) in the Taber abrasion test.
- a ⁇ value is determined according to ASTM D1044 by mounting a Taber abrasion tester with abrasion wheels CS-10F, measuring the haze after 1,000 rounds under a load of 500 grams (g), and calculating a difference ( ⁇ ) between haze values before and after the test.
- the laminate c can have ⁇ Hz of up to 5.0%, specifically, up to 3.0%, and more specifically, less than 2.0%.
- the present laminate is also characterized by adhesion.
- An index of adhesion is given by the adhesion test of (A) immersing in ion exchanged water at 65 °C for 10 days according to ASTM D870 and measuring adhesion by the tape test of ASTM D3359, Test Method B and by the adhesion test of (B) immersing in ion exchanged water at 100°C for 2 hours according to ASTM D870 and measuring adhesion by the tape test of ASTM D3359, Test Method B.
- the sample is evaluated good in adhesion when less than or equal to 3% of the coating area is removed after both of the above tests (A) and (B).
- the present laminate is further characterized by weather resistance.
- An index of weather resistance is given by a weathering test to see whether or not a coating is kept intact, that is, whether or not a coating is cracked or delaminated, and also whether or not a laminate is yellowed.
- the weathering test is carried out by using Eyesuper UV tester W-151 (Iwasaki Electric Co., Ltd.), and repeating cycles consisting of [black panel temperature 63 °C, humidity 50% RH, illuminance 50 milliwatts per square centimeter (mW/cm ), water spray intervals of 10 seconds per hour (sec/hour) for 5 hours] and [black panel temperature 30°C, humidity 95% relative humidity (RH) for one hour].
- Those samples whose coating exhibits neither cracking nor delamination or whose substrate exhibits a change of yellowing index of 3.0 or less after 30 cycles are regarded as passing the test.
- Examples of the laminate are given below by way of illustration and not by way of limitation. In Examples, all parts and percentages are by weight unless otherwise indicated. Viscosity is measured at 25°C according to JIS Z8803. Mw is a weight average molecular weight as measured by GPC versus polystyrene standards. GPC stands for gel permeation chromatography, 1H-NMR for proton nuclear magnetic resonance spectroscopy, and IR for infrared absorption spectroscopy.
- the reaction solution was cooled to room temperature, passed through a silica gel-loaded column, and concentrated in vacuum, obtaining 41.8 g of a compound S3 having the following formula (15).
- the compound S3 can have a UV absorbing group content of 41% as calculated from formula (15).
- KBM-5103 (Shin-Etsu Chemical Co., Ltd.,
- acryloyloxypropyltrimethoxysilane 142 g
- the liquid was concentrated by vacuum distillation, obtaining a hydrolytic condensate of trifunctional acrylic silane ("5103 condensate”) as colorless clear liquid. It had a nonvolatile content of 99.3% and a Mw of 1,900.
- Reference Example 2 (Organic/inorganic hybrid acrylate; colloidal silica surface treated with acrylic silane)
- acryloyloxypropylmethyldimethoxysilane 155 g was combined with 0.15 g of p- methoxyphenol, 3.9 g of ethanol, and 1.9 g of cation exchange resin Purolite® CT-169DR. The mixture was thoroughly stirred. Then 25.5 g of deionized water was added to the mixture, which was stirred at room temperature for 1 hour, heated at 70°C and stirred for a further 2 hours. The reaction mixture was concentrated by vacuum distillation and passed through a mesh filter to remove the cation exchange resin, obtaining a hydrolytic condensate of difunctional acrylic silane ("5102 condensate”) as colorless clear liquid. It had a nonvolatile content of 98.8% and a viscosity of 129 milliPascal-second (mPa- s).
- Photo-curable coating compositions (ocl to oc4, oc7 to ocl 1) were prepared by mixing a reactive UV absorber (A) which was selected from compounds S 1 and S2 of Synthesis Examples 1 and 2 with a multifunctional (meth)acrylate (B), a photopolymerization initiator (C) and other components in the amounts shown in Table 1 at room temperature for
- A-M403 dipentaerythritol penta- and hexaacrylate available under the trade name Aronix
- HDDA 1,6-hexane diol diacrylate available under the trade name HDDA from Daicel-
- U-4HA urethane acrylate of non-yellowing type available under the trade name U-4HA from Shin-Nakamura Chemical Co., Ltd.
- 5103 condensate hydrolytic condensate of KBM-5103 (trade name of 3-acryloxypropyl trimethoxysilane from Shin-Etsu Chemical Co., Ltd.), see Reference Example 1 5103-treated silica: organic/inorganic hybrid acrylate dispersion, that is, dispersion in
- organic solvent of colloidal silica surface treated with KBM-5103 (trade name of
- KBM-5102 hydrolytic condensate of KBM-5102 (trade name of 3- acryloxypropylmethyldimethoxysilane from Shin-Etsu Chemical Co., Ltd.), see
- TPO 2,4,6-trimethylbenzoyldiphenylphosphine oxide available as
- T928 2-(2H-benzotriazol-2-yl)-6-( 1 -methyl- 1 -phenylethyl)-4-( 1,1,3,3- tetramethylbutyl)phenol available as UV absorber under the trade name
- R93 2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole available as UV absorber under the trade name RUVA93 from Otsuka Chemical Co., Ltd.
- T400 a mixture of 85% the reaction product of 2-(4,6-bis(2,4-dimethylphenyl)- 1,3,5- triazin-2-yl)-5-hydroxyphenyl with oxirane ((C 10 -C 16 , mainly C12-C13 alkyloxy)methyl oxirane) and 15% l-methoxy-2-propanol, available as UV absorber under the trade name TINUVIN 400 from BASF
- Ti0 2 a dispersion of surface treated titanium oxide in organic solvent, available under the trade name Nano-Tek RTTDNB 15 wt%-E88 from C.I. Kasei Co., Ltd.
- HALS 1, 2,2,6, 6-pentamethyl-4-piperidinyl methacrylate available under the trade name
- KP341 polyether- modified silicone available under the trade name KP341 from Shin-
- PGM propylene glycol monomethyl ether
- Photo-curable coating composition (ocl) in Preparation Example 1 was flow coated onto a cleaned surface of a LexanTM polycarbonate plate (150 mm by 150 mm by 4 mm thick) and heated at 80°C for 5 minutes for evaporating off the solvent. Using a conveyor type UV exposure unit equipped with a 120 watts(W) high-pressure mercury lamp, the coating was exposed to UV radiation in a nitrogen atmosphere so as to provide an integral dose of 600 mJ/cm at 365 nm. In this way, a cured film having a thickness of about 9 to 11 ⁇ was obtained as intermediate layer (II).
- plasma polymerization was carried out to deposit a film composed of silicon, oxygen, carbon and hydrogen on the cured film as plasma layer, yielding a laminate.
- the substrate having a cured film of the photo- curable coating composition formed thereon was cleaned by manual operation using an isopropyl alcohol/deionized water-drenched lint-free cloth.
- Plasma polymerization was then carried out in a vacuum chamber by the continuous, 2-sided expanding thermal plasma process (CD. Iacovangelo et al., "Expanding thermal plasma deposition system", US Patent Application 2005/0202184, March 8, 2005).
- Two plasma coating stations consisted of arrays of expanding thermal plasma sources that issued argon plasma jets at supersonic speeds.
- the plasma jets expanded in the plasma coating stations and reacted with an organosilicon reagent and optional oxidizing agent that were injected directly into the chamber.
- the organosilicon reagent used herein was octamethylcyclotetrasiloxane (by Gelest Inc.), and the oxidizing agent was 99% pure oxygen of industrial grade (by Airgas Inc.).
- the substrate was continuously transported through the chamber and heated at approximately 40-70°C before entering the coating stations.
- Variables of the plasma process included the heating temperature of the preheat chamber, linear transportation speed, flow rates of organosilicon, oxygen and argon, and current/plasma source.
- the process pressure was in a range of 30 to 70 milliTorr (mTorr).
- Laminates were manufactured by the same procedure as in Example 1, using photo-curable coating compositions (ocl) to (oc4) in Preparation Examples 1 to 4. The laminates were evaluated by the following tests, with the results shown in Table 3.
- Laminates were manufactured by the same procedure as in Example 1, using photo-curable coating compositions (ocl) and (oc7) to (al l) in Preparation Example 1 and Comparative Preparation Examples 1 to 5. It is noted that in Comparative Example 6, plasma layer was omitted. The laminates were evaluated by the following tests, with the results shown in Table 4.
- a laminate sample was measured for haze by a haze meter NDH5000SP (Nippon Denshoku Industries Co., Ltd.).
- Abrasion resistance was analyzed according to ASTM D1044 by mounting a Taber abrasion tester with wheels CS-10F, measuring a haze after 1,000 rounds under a load of 500 g, and calculating a haze difference (AHz) before and after the test.
- AHz haze difference
- a delta haze (AHz) value of 2.0% or less is regarded acceptable.
- Adhesion was analyzed by a cross-hatch adhesion test according to ASTM D3359 Test Method B, specifically by scribing the laminate with a razor along 11 longitudinal and 11 transverse lines at a spacing of 1 mm to define 100 square sections, tightly attaching adhesive tape thereto, rapidly pulling back the adhesive tape at an angle of 90°, and calculating the percent area of coating sections delaminated.
- An initial adhesion i.e., 100% - percent of coating area delaminated
- the laminate was immersed in deionized water at 65 °C for 10 days before it was examined by the same adhesion test (ASTM D3359 Test Method B) as the initial adhesion.
- a post-immersion adhesion (i.e., 100% - percent of coating area delaminated) value of at least 97% is regarded acceptable.
- a weathering test was carried out by means of Eyesuper UV tester W-151 (Iwasaki Electric Co., Ltd.) which operated one cycle of [black panel temperature 63°C, humidity 50% RH, illuminance 50 mW/cm , water spray intervals of 10 sec/hour for 4 hours] and [black panel temperature 30°C, humidity 95% RH for one hour]. The test repeated 30 and 70 cycles.
- a yellowing index (YI) was measured according to JIS K7103 before and after the test, from which a change of yellowing index ( ⁇ YI) was computed.
- the weathered laminate was also examined for cracks and delamination with naked eyes or under a microscope (250x magnifying power). A sample that has experienced a change of yellowing index ( ⁇ YI) of 3.0 or less after 30 cycles and no external appearance defects (such as cracks or delamination) is regarded acceptable.
- Preheating temperature (heater surface, °C) 350 375
- the laminates herein are substantially improved in abrasion resistance.
- Examples 1 to 7 including plasma layer showed ⁇ Hz values of 2.0% or less (good abrasion resistance), whereas Comparative Example 6 without plasma layer showed a ⁇ Hz value of 7.1% (poor abrasion resistance).
- Examples 1 to 7 showed a ⁇ Hz value of 2.0% or less and a ⁇ YI value after 30 cycles of 3.0 or less, specifically 2.0 or less (minimal yellowing index change).
- Comparative Examples 1 and 2 showed a ⁇ Hz value of 2.0% or less, but a ⁇ YI value of more than 10 and delamination because the intermediate layer (II) contained no or a reduced amount of UV absorber.
- Comparative Example 5 using highly compatible liquid UV absorber showed delamination in the weather resistance test of 30 cycles because the absorber was free of a binder-reactive group probably due to bleed-out of the UV absorber. All the properties that the inventive laminate should possess are not met by Comparative Examples.
- the oxygen permeability measured was 195 cc/m /day for the polycarbonate substrate, 168 cc/m /day for the laminate having only intermediate layer (II) of the photo-curable coating composition stacked thereon, and 158 cc/m /day for the laminate having both intermediate layer (II) and plasma layer stacked thereon. (FIG. 4)
- An embodiment can comprise an organic resin laminate (e.g., having a high level of abrasion resistance and weather resistance), comprising an organic resin substrate and a multilayer coating system on one or both surfaces of the substrate.
- the multilayer coating system can include a plasma layer which is a hard coating obtained from plasma polymerization of an organosilicon compound, and an intermediate layer (II) which is a cured coating of a wet coating composition, the intermediate layer (II) having one surface disposed contiguous to the plasma layer and another surface disposed contiguous to the organic resin substrate.
- the wet coating composition comprises (A) a specific reactive UV absorber, (B) a multi-functional (meth)acrylate, and (C) a photopolymerization initiator.
- Another embodiment of a method for manufacturing an organic resin laminate comprises furnishing an organic resin substrate, applying a wet coating composition to a surface of the substrate to form an intermediate layer (II), and effecting plasma polymerization of an organosilicon compound to form a plasma layer on the intermediate layer (II).
- the wet coating composition comprises (A) a specific reactive UV absorber, (B) a multi-functional (meth)acrylate, and (C) a photopolymerization initiator.
- the substrate is furnished by an extrusion, co-extrusion or laminating technique.
- the wet coating composition is brought in physical contact with a substrate to form a monolithic substrate.
- the substrate is furnished by extruding a plastic material (e.g., transparent plastic material, specifically optically clear plastic material) and a cap layer.
- a plastic material e.g., transparent plastic material, specifically optically clear plastic material
- the substrate is furnished by laminating a plastic material (e.g., transparent plastic material, specifically optically clear plastic material) and a cap layer.
- Embodiment 1 A method of making an organic resin laminate, comprising: applying a wet coating to an organic resin substrate to form to form an intermediate layer (II) on the substrate, wherein the wet coating comprises a multi-functional (meth)acrylate, a photopolymerization initiator, and a reactive UV absorber having the general formula (1):
- Y 1 a 2 are each independently a substituent group of the general formula (2):
- Embodiment 2 The method of Embodiment 1, wherein the first oxygen flow rate of less than or equal to 100 seem per plasma source.
- Embodiment 3 The method of Embodiment 2, wherein the first oxygen flow rate of less than or equal to 50 seem per plasma source.
- Embodiment 4 The method of Embodiment 3, wherein the first oxygen flow rate of less than or equal to 10 seem per plasma source.
- Embodiment 5 A method of making an organic resin laminate, comprising: applying a wet coating to an organic resin substrate to form an intermediate layer (II) on a substrate, wherein the wet coating comprises a multi-functional (meth)acrylate, a photopolymerization initiator, and a reactive UV absorber having the general formula (1):
- Y 1 and Y 2 are each independently a substituent group of the general formula (2):
- Embodiment 6 The method of any one of Embodiments 1 - 5, further comprising, depositing a second plasma coating on the first plasma coating, wherein the second plasma coating and the first plasma coating form a plasma layer, and wherein the second plasma coating is deposited using a second oxygen flow rate of greater than or equal to 250 seem per plasma source.
- Embodiment 7 The method of Embodiment 6, wherein the second oxygen flow rate is greater than or equal to 400 seem per plasma source.
- Embodiment 8 The method of Embodiment 7, wherein the second oxygen flow rate is greater than or equal to 800 seem per plasma source.
- Embodiment 9 The method of any one of Embodiments 1 - 8, wherein the first plasma coating is deposited using expanding thermal plasma deposition.
- Embodiment 10 The method of any of Embodiments 1 - 9, further comprising flashing off solvent from the wet coating before the UV curing.
- Embodiment 11 The method of Embodiment 10, wherein the flashing off comprises heating the coated substrate to greater than or equal to 60°C.
- Embodiment 12 The method of Embodiment 11, wherein the flashing off comprises heating the coated substrate to greater than or equal to 70°C.
- Embodiment 13 The method of any one of Embodiments 1 - 12, further comprising molding the substrate prior to applying the wet coating, wherein the organic resin substrate comprises polycarbonate, a blend comprising polycarbonate, or a copolymer comprising polycarbonate.
- Embodiment 14 The organic resin laminate formed by the method of any of Embodiments 1 - 13.
- Embodiment 15 The laminate of Embodiment 14, wherein X is a group having the general formula (3) or (4):
- * 1 bonds to the oxygen in formula (1), *2 bonds to T in formula (1), *3 each independently is hydrogen or bonds to T in formula (1) directly or via a divalent, linear or branched, saturated hydrocarbon group which may be separated by at least one element of oxygen, nitrogen, sulfur, and phosphor, at least one *3 bonds to T directly or via a divalent, linear or branched, saturated hydrocarbon group which may be separated by at least one element of oxygen, nitrogen, sulfur, and phosphor; and Q is a group having the general formula (
- Embodiment 16 The laminate of any of Embodiments 14 - 15, wherein in formula (1), R 1 , R2 and R 3 are each independently hydrogen or methyl, X is a group of formula (3), Q is a group of formula (6), m is 2, and n is 1.
- Embodiment 17 The laminate of any one of Embodiments 14 - 16, wherein the multi-functional (meth)acrylate (B) comprises a hydrolyzate and/or condensate of a (meth)acrylic functional alkoxysilane.
- Embodiment 18 The laminate of any one of Embodiments 14 - 17, wherein the multi-functional (meth)acrylate (B) further comprises at least one member selected from the group consisting of dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tris(2-(meth)acryloxyalkyl) isocyanurates, urethane poly(meth)acrylate compounds having at least five radical polymerizable unsaturated double bonds per molecule, and polyester poly(meth)acrylate compounds having at least five radical polymerizable unsaturated double bonds per molecule.
- the multi-functional (meth)acrylate (B) further comprises at least one member selected from the group consisting of dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tris(2-(meth)acryloxyalkyl) isocyanurates, urethan
- Embodiment 19 The laminate of any one of Embodiments 14 - 18, wherein the laminate shows a value of at least 97% in an adhesion test of immersing in ion exchanged water at 65°C for 10 days according to ASTM D870 and measuring adhesion by a tape test according to ASTM D3359-09, Test Method B.
- Embodiment 20 The laminate of any one of Embodiments 14 - 19, wherein the first plasma layer, the second plasma layer or both the first plasma layer and the second plasma layer, contains silicon, oxygen, carbon and hydrogen, and is formed by plasma polymerization of an organosilicon compound.
- Embodiment 21 The laminate of any one of Embodiments 14 - 20, comprising the second plasma coating and wherein the plasma layer has a total thickness in the range of 2.5 to 5.0 ⁇ .
- Embodiment 22 The laminate of Embodiment 21, comprising the second plasma coating and wherein the plasma layer has a total thickness in the range of 2.5 to 4.0 ⁇ .
- Embodiment 23 The laminate of any one of Embodiments 14 - 22, wherein the organic resin substrate comprises polycarbonate, a blend comprising
- polycarbonate or a copolymer comprising polycarbonate.
- Embodiment 24 The laminate of any of Embodiments 14 - 23,
- the plasma layer has a Young's Modulus of greater than or equal to 3 GPa as determined by nanoindentation with a maximum load of 1 mN
- Embodiment 25 The laminate of Embodiment 24, comprising the second plasma coating, and wherein the plasma layer has a Young's Modulus of 3 GPa to 40 GPa as determined by nanoindentation with a maximum load of 1 milliNewtons (mN).
- mN milliNewtons
- Embodiment 26 The laminate of Embodiment 25, comprising the second plasma coating, and wherein the plasma layer has a Young's Modulus of 3 GPa to 15 GPa as determined by nanoindentation with a maximum load of 1 mN.
- Embodiment 27 An organic resin laminate comprising: an organic resin substrate and a multilayer coating system on a surface of the substrate; said multilayer coating system including a plasma layer obtained from polymerization of an organosilicon compound and an intermediate layer (II) which is a UV cured coating of a coating
- the coating composition comprising (A) a reactive UV absorber, (B) a multifunctional (meth)acrylate, and (C) a photopolymerization initiator, the reactive UV absorber having the general formula (1):
- Y 1 and Y 2 are each independently a substituent group of the general formula (2):
- Embodiment 28 The laminate of Embodiment 27, wherein X is a group having the general formula (3) or (4):
- * 1 bonds to the oxygen in formula (1), *2 bonds to T in formula (1), *3 each independently is hydrogen or bonds to T in formula (1) directly or via a divalent, linear or branched, saturated hydrocarbon group which may be separated by at least one element of oxygen, nitrogen, sulfur, and phosphor, at least one *3 bonds to T directly or via a divalent, linear or branched, saturated hydrocarbon group which may be separated by at least one element of oxygen, nitrogen, sulfur, and phosphor; and Q is a group having the general formula (
- Embodiment 29 The laminate of Embodiment 27 or 28, wherein in formula (1), R 1 , R2 and R 3 are each independently hydrogen or methyl, X is a group of formula (3), Q is a group of formula (6), m is 2, and n is 1.
- Embodiment 30 The laminate of any one of Embodiments 27 to 29, herein the multi-functional (meth)acrylate (B) comprises a hydrolyzate and/or condensate of a (meth)acrylic functional alkoxysilane.
- Embodiment 31 The laminate of any one of Embodiments 27 to 30, wherein the multi-functional (meth)acrylate (B) further comprises at least one member selected from the group consisting of dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tris(2-(meth)acryloxyalkyl) isocyanurates, urethane poly(meth)acrylate compounds having at least five radical polymerizable unsaturated double bonds per molecule, and polyester poly(meth)acrylate compounds having at least five radical polymerizable unsaturated double bonds per molecule.
- the multi-functional (meth)acrylate (B) further comprises at least one member selected from the group consisting of dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tris(2-(meth)acryloxyalkyl) isocyanurates, urethane
- Embodiment 32 The laminate of any one of Embodiments 27 to 31, wherein the plasma layer contains silicon, oxygen, carbon and hydrogen, and is formed by plasma polymerization of an organosilicon compound.
- Embodiment 33 The laminate of any one of Embodiments 27 to 32, wherein the plasma layer has a total thickness in the range of 2.5 to 5.0 ⁇ .
- Embodiment 34 The laminate of Embodiment 33 , wherein the plasma layer has a total thickness in the range of 2.5 to 4.0 ⁇ .
- Embodiment 35 The laminate of any one of Embodiments 27 to 34, which shows a value of at least 97% in an adhesion test of immersing in ion exchanged water at 65°C for 10 days according to ASTM D870 and measuring adhesion by a tape test according to ASTM D3359-09, Test Method B.
- Embodiment 36 The laminate of any one of Embodiments 27 to 35, wherein the organic resin substrate is a molded substrate comprising polycarbonate, a blend comprising polycarbonate, or a copolymer comprising polycarbonate.
- Embodiment 37 The laminate of any of Embodiments 27 - 36, wherein the plasma layer comprises a first plasma coating and a second plasma coating, and wherein the outermost plasma layer has a Young's Modulus of greater than or equal to 3 GPa as determined by nanoindentation with a maximum load of 1 milliNewton (mN).
- the plasma layer comprises a first plasma coating and a second plasma coating
- the outermost plasma layer has a Young's Modulus of greater than or equal to 3 GPa as determined by nanoindentation with a maximum load of 1 milliNewton (mN).
- Embodiment 38 The laminate of Embodiment 37, wherein the plasma layer has a Young's Modulus of 3 GPa to 40 GPa as determined by nanoindentation with a maximum load of 1 mN.
- Embodiment 39 The laminate of Embodiment 38, wherein the plasma layer has a Young's Modulus of 3 GPa to 15 GPa as determined by nanoindentation with a maximum load of 1 mN.
- Embodiment 40 An organic resin laminate, the comprising: an organic resin substrate and a multilayer coating system on a surface of the substrate, said multilayer coating system including: a plasma layer formed from polymerization of an organosilicon compound; and an intermediate layer (II) which is a UV cured coating of a reactive UV absorber, a multi-functional (meth)acrylate, and a photopolymerization initiator; wherein the laminate has a Young's Modulus of greater than or equal to 3 GPa as determined by nanoindentation with a maximum load of 1 mN.
- Embodiment 41 The laminate of Embodiment 40, which shows a value of at least 97% in an adhesion test of immersing in ion exchanged water at 65 °C for 10 days according to ASTM D870 and measuring adhesion by a tape test according to ASTM D3359- 09, Test Method B.
- Embodiment 42 An agent used for an automotive window, wherein the agent comprises an organic resin substrate and a multilayer coating system on a surface of the substrate, the multilayer coating system including an outermost plasma layer formed from polymerization of an organosilicon compound and an intermediate layer which is a UV cured coating of a coating composition, the intermediate layer (II) disposed between the plasma layer and the organic resin substrate; the wet coating comprises a multi-functional
- Y 1 and Y 2 are each independently a substituent group of the general formula (2):
- the term "laminate” refers to a structure comprising a plurality of layers which are formed by appropriate processes.
- the processes include, for example, extrusion, co-extrusion, adhesive film, film insertion molding, wet coating, plasma deposition, lamination, and processes of arbitrary combination of the foregoing.
- the notation (C n -C m ) means a group containing from n to m carbon atoms per group.
- UV refers to the ultraviolet region of the electromagnetic spectrum.
- Mw refers to a weight average molecular weight as measured by gel permeation chromatography (GPC) versus polystyrene standards.
- GPC gel permeation chromatography
- (meth)acrylate refers collectively to acrylate and methacrylate. All ranges disclosed herein are inclusive of the endpoints, and the endpoints are
Abstract
Description
Claims
Priority Applications (7)
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EP15797402.3A EP3155037B1 (en) | 2014-06-12 | 2015-06-08 | Organic resin laminate |
KR1020167030684A KR102231452B1 (en) | 2014-06-12 | 2015-06-08 | Organic resin laminate |
JP2016553427A JP6269853B2 (en) | 2014-06-12 | 2015-06-08 | Organic resin laminate |
US16/219,260 US20190112441A1 (en) | 2014-06-12 | 2018-12-13 | Organic resin laminate |
US17/072,401 US20210032429A1 (en) | 2014-06-12 | 2020-10-16 | Organic resin laminate |
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WO2015189762A2 (en) * | 2014-06-12 | 2015-12-17 | Sabic Global Technologies B.V. | Organic resin laminate |
JP6915405B2 (en) * | 2017-06-29 | 2021-08-04 | 信越化学工業株式会社 | Poly (meth) acrylate and coating compositions and coating articles containing it |
CN115043974A (en) * | 2017-06-30 | 2022-09-13 | 阿莱恩技术有限公司 | 3D printing compound made of single resin by patterned exposure |
JP2020032759A (en) * | 2018-08-27 | 2020-03-05 | 株式会社小糸製作所 | Method for manufacturing resin-made composite module for vehicle |
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CN106574066A (en) | 2017-04-19 |
US20210032429A1 (en) | 2021-02-04 |
WO2015189762A3 (en) | 2016-04-14 |
US20170198110A1 (en) | 2017-07-13 |
CN106574066B (en) | 2020-03-03 |
EP3155037B1 (en) | 2019-07-24 |
JP2017511399A (en) | 2017-04-20 |
EP3155037A2 (en) | 2017-04-19 |
KR102231452B1 (en) | 2021-03-23 |
JP6269853B2 (en) | 2018-01-31 |
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